Self-Assembly of Aromatic-Functionalized Amphiphiles: The Role and Consequences of Aromatic−Aromatic Noncovalent Interactions in Building Supramolecular Aggregates and Novel Assemblies

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This feature article presents an overview of a study of several different aromatic-functionalized amphiphilesfatty acid and phospholipid derivatives. These amphiphiles form organized assemblies when the fatty acids are spread as monolayers at the air−water interface or when the phospholipids are dispersed in aqueous solutions. For a wide range of aromatic chromophorestrans-stilbene derivatives and a series of “vinylogues” (1,4-diphenyl-1,3-butadiene and 1,6-diphenyl-1,3,5-hexatriene), diphenylacetylenes, and azobenzenes such as phenyl, biphenyl, and terphenyl derivatives and modified stilbenes (styryl thiophenes and styryl naphthalenes)assembly formation is accompanied by formation of aggregates of the aromatic groups. Results of experimental studies and simulations indicate that in many cases the aromatics form a small, stable “unit aggregate” characterized by strong “noncovalent” edge-to-face interactions among adjacent aromatics. Although the unit aggregates exhibit characteristic spectral shifts and strong induced circular dichroism indicating a chiral “pinwheel” aggregate structure, they may be packed together in pure films or dispersions to form an extended glide or herringbone structure. Although the “pinwheel” unit aggregate and the extended glide structure is favored for the majority of aromatics studied, for certain aromatics (styrenes, styrylthiophenes, and α-styrylnaphthalenes) a translation layer, characterized by face-to-face noncovalent interactions, is preferred. The glide or herringbone aggregates are readily distinguished from the translation aggregates by different spectral signatures and different photochemical and photophysical behavior. Factors controlling the type of aggregate and hence extended structure formed from different aromatic functionalized aromatics include shape and steric factors and strength of the competing noncovalent edge-face and face-face interactions.